Photocatalytic fixation of NOx in soils.

Nitrogen oxides (NOx = NO + NO2) are important atmospheric pollutants that are directly harmful to human health. Recently in urban and industrial areas, synthetic materials have been developed and deployed to photocatalytically oxidize NOx to nitrate (NO3-) in order to improve air quality. We show that the natural presence of small amounts (≤5%) of titanium oxides, such as anatase and rutile, can also drive NOx oxidation to nitrate in soils under UV-visible irradiation. The NO uptake coefficients ranged between 0.1 × 10-6 for sandy soils to 6.4 × 10-5 in the case of tropical clay soils; the latter comparable in efficiency to current industrial man-made catalysts. This photocatalytic N-fixation mechanism offers a new strategy for NOx mitigation from the atmosphere by transforming it into nitrate, and simultaneously provides an energy efficient source of essential fertilizer to agriculture.

Unexpectedly high indoor hydroxyl radical concentrations associated with nitrous acid.

The hydroxyl (OH) radical is the most important oxidant in the atmosphere since it controls its self-oxidizing capacity. The main sources of OH radicals are the photolysis of ozone and the photolysis of nitrous acid (HONO). Due to the attenuation of solar radiation in the indoor environment, the possibility of OH formation through photolytic pathways indoors has been ignored up to now. In the indoor air, the ozonolysis of alkenes has been suggested as an alternative route of OH formation. Models and indirect measurements performed up to now according to this hypothesis suggest concentrations of OH radicals on the order of 10(4)-10(5) molecules per cubic centimeter. Here, we present direct measurements of significant amounts of OH radicals of up to 1.8⋅10(6) molecules per cubic centimeter during an experimental campaign carried out in a school classroom in Marseille. This concentration is on the same order of magnitude of outdoor OH levels in the urban scenario. We also show that photolysis of HONO is an important source of OH radicals indoors under certain conditions (i.e., direct solar irradiation inside the room). Additionally, the OH concentrations were found to follow a linear dependence with the product J(HONO)⋅[HONO]. This was also supported by using a simple quasiphotostationary state model on the OH radical budget. These findings force a change in our understanding of indoor air quality because the reactivity linked to OH would involve formation of secondary species through chemical reactions that are potentially more hazardous than the primary pollutants in the indoor air.

Characterisation and calibration of active sampling Solid Phase Microextraction applied to sensitive determination of gaseous carbonyls.

A characterisation of a system designed for active sampling of gaseous compounds with Solid Phase Microextraction (SPME) fibres is described. This form of sampling is useful to automate sampling while considerably reducing the sampling times. However, the efficiency of this form of sampling is also prone to be affected by certain undesirable effects such as fibre saturation, competition or displacement effects between analytes, to which particular attention should be paid especially at high flow rates. Yet, the effect of different parameters on the quantitivity of the results has not been evaluated. For this reason, in this study a careful characterisation of the influence of the parameters involved in active sampling SPME has been performed. A versatile experimental set-up has been designed to test the influence of air velocities and fluid regime on the quantitivity and reproducibility of the results. The mathematical model applied to the calculation of physical parameters at the sampling points takes into consideration the inherent characteristics of gases, distinctive from liquids and makes use of easily determined experimental variables as initial/boundary conditions to get the model started. The studies were carried out in the high-volume outdoor environmental chambers, EUPHORE. The sample subjected to study was a mixture of three aldehydes: pentanal, hexanal and heptanal and the determination methodology was O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine hydrochloride (PFBHA) on-fibre derivatisation. The present work proves that the determination procedure is quantitative and sensitive, independent from experimental conditions: temperature, relative humidity or ozone levels. With our methodology, the influence on adsorption of three inter-related variables, i.e., air velocity, flow rate and Reynolds numbers can be separated, since a change can be exerted in one of them while keeping the others constant.

Atmospheric photosensitized heterogeneous and multiphase reactions: from outdoors to indoors.

This proposal involves direct photolysis processes occurring in the troposphere incorporating photochemical excitation and intermolecular energy transfer. The study of such processes could provide a better understanding of ·OH radical formation pathways in the atmosphere and in consequence, of a more accurate prediction of the oxidative capacity of the atmosphere. Compounds that readily absorb in the tropospheric actinic window (ionic organic complexes, PAHs, aromatic carbonyl compounds) acting as potential photosensitizers of atmospheric relevant processes are explored. The impact of hotosensitation on relevant systems which could act as powerful atmospheric reactors,that is, interface ocean-atmosphere, urban and forest surfaces and indoor air environments is also discussed.

Photolysis and heterogeneous reaction of coniferyl aldehyde adsorbed on silica particles with ozone.

The pseudo-first-order loss of coniferyl aldehyde, adsorbed on silicon dioxide particles, upon heterogeneous ozonolysis was monitored at various ozone mixing ratios in the absence and presence of simulated sunlight. For the first time we investigated the effect of light on the heterogeneous ozonolysis of coniferyl aldehyde adsorbed on silica particles. We found that UV-VIS light (λ>300 nm) does not impact the degradation of coniferyl aldehyde by ozone but induces an additional, slow photolysis of the aldehyde with a photolytic rate constant of ~10(-5) s(-1). In both cases, that is, in presence and/or absence of light, the heterogeneous ozonation kinetics are well described by an immediate gas-surface reaction formalism with light-independent rate constants of k(2nd)=(7.2±0.9)×10(-19) cm(3) molec(-1) s(-1) and (7.6±1.7)×10(-19) cm(3) molec(-1) s(-1) in the absence and presence of light, respectively. Five oxidation products: glycolic acid, oxalic acid, vanillin, vanillic acid and 3,4-dihydroxybenzoic acid were identified and confirmed by their corresponding standards. Vanillin and vanillic acid absorb light in the region λ>300 nm and thus can further participate in the direct and indirect photolysis processes of atmospheric relevance. A reaction mechanism is proposed in order to elucidate the ozonolysis reaction and to explain the reaction products.